CONTACT ANGLES:

Laplace-Young Equation and

Dupre-Young
Dupre Young Relationship.
R. L. Cerro
Chemical and Materials Engineering
The Universityy of Alabama in Huntsville

Santa Fe
16 de Abril de 2010
Acknowledgements:
„ Dr.Javier Fuentes (PhD-2003)-
Univ. Simon Bolivar,, Caracas,,
VE. School of Chemical
Engineering and Analytical
Science, The Univ. of
Manchester, UK
„ D El
Dr. Elena Diaz
Di Martin
M ti (PhD-
(PhD
2004)-Depto. de Ing. Quimica &
Textil, Universidad de
Salamanca, Spain.
„ Dr Michael D.
Dr. D Savage,
Savage Physics
and Astronomy Dept. Leeds
University, UK.
 OUTLINE OF PRESENTATION

●Introduction/Motivation: What is wetting? Why is it

important?
●The
Th F ll A
Fully-Augmented
d Young-Laplace
Y L l Equation
E i
● Young’s relationship: static contact angles.
● A 2D sessile drop = puddle.
● C ill
Capillary rise
i
● The future behind
 Wetting applications: boiling and condensation

Cooling electronic circuits

Heat
eat pipes
p pes rely
ey oon
boiling and
condensation of the
cooling liquid.
Micro heat pipes are
Micro-heat
about 1 mm in
diameter.
 Super-hydrophobic
Super hydrophobic surfaces:

Super-hydrophobicity is the result

of chemistry and structure.
Self-cleaning
Self cleaning superhydrophobic surfaces
„ Structure & Chemistry
Wetting precedes adhesion:

Feet of a geico and

the threads of a
mussel are examples
of natural adhesives.
Vapor/Liquid Interfaces
Interfaces are:
1.Diffuse (3D)
2.Dynamic
3 Asymmetric
3.Asymmetric
 Static Contact Angles:Young relationship
and the Young-Laplace
Young Laplace equation.
equation
WETTING: The contact angle for a
th
three-phase
h region
i isi the
th main i
variable in Young’s equation.

THOMAS YOUNG,, 1805

CAPILLARITY: The curvature of σ SV − σ SL = σ LV cos θ

the interface and the specific
interfacial free energy of the
interface, are related to the
pressure jump between the
inside and outside of a liquid
drop.
YOUNG-LAPLACE EQUATION

( pin − pout ) − 2 H σ VL = 0
 Young-Laplace Equation in Differential Form:

pinside = poutside − 2 H σ
1 1
2H = + {R1 , R2 :principal radius of curvature
R1 R2

pinside = ρin g z ; poutside = ρ out g z ρin g zo

⎧ 2 ⎫
⎪ d z dz ⎪
⎪ d x2 ⎪
g z ( ρin − ρout ) = ρin g ( z − zo ) = ⎨ 3/2
+ dx
1/2 ⎬ σ
⎪ ⎡ ⎛ dz ⎞ ⎤ ⎡ ⎛ dz ⎞1/2 ⎤ ⎪
1/2

⎪ ⎢1 + ⎜ dx ⎟ ⎥ z ⎢1 + ⎜ ⎟ ⎥ ⎪
⎩ ⎢⎣ ⎝ ⎠ ⎥⎦ ⎢⎣ ⎝ dx ⎠ ⎥⎦ ⎭
The equation of Young and Laplace:
Historical introduction.
introduction
„ Thomas Young [Phil. Trans. Roy. Soc, vol 95, pp. 65-87
(1805)]
„ Born in Milverton, Somerset (1773) youngest of 10 children
„ Studied medicine in London, Edinburgh and physics in Gottingen
„ Entered Emmanuel College in Cambridge and practiced medicine in London
„ A
Appointed
i d professor
f off Natural
N l philosophy
hil h at Royal
R l Institution
I i i (1801)
„ Foreign associate in French Academy of Sciences (1827)
„ Wave theory of light, Young modulus, translated hieroglyphs, etc.
„ Pierre Simon de Laplace [Ouvres Completes,
Completes pp.
pp 394
(1807)]
„ Born in Normandy, 1749.
„ Univ. of Caen (16 years old)
„ U i off Paris
Univ. P i (18 years old).
ld)
„ Rejected by Acad. of Sciences (22 yr old)
„ Accepted to Berlin Acad. of Sci. (24 yr)
„ Young never wrote the equation!
„ “On the attribution of an equation of capillarity to Young and Laplace”, Pujado, Huh
and Scriven, JCISvol. 38, pp 662-663, (1972).
Surfaces in 3D space:
Surface geometry

„ Surfaces in 3D space:
„ Orientable in space
„ Locally have two sides
„ Globally have in general two sides with famous
exceptions (Mobius strip)
„ If they are closed
closed, separate an inside space
from an outside space with famous exceptions
(Klein bottle)
„ They have shape
„ Globaly shape distinguishes a torus from a sphere
„ Locally it is distinguished by its curvature
 Surface curvature
1. Location: a point on the surface is described by
the vector R
R.
2. Orientation: the top and bottom are described
by a unit vector n, normal to the surface
3. Two tangents unit vectors, a1 and a2 are
normal to each other and both are normal to
R = R ( x, y , z ) the vector n.
4. Points on the
h surface
f can be
b described
d b d on the
h
r = R ( u1 , u2 ) basis of a two dimensional system.
κ1 = 1/ R1 ; κ 2 =1/ R2 5. The rate of change of orientation (normal)
corresponds
d to
t th
the iintuitive
t iti notion
ti off shape.
h
1⎛ 1 1 ⎞ 1
H = ⎜ + ⎟ = ( κ1 + κ 2 ) 6. Curvature is defined as the inverse, 1/R, of the
2 ⎝ R1 R2 ⎠ 2
radius of a circle tangent to the surface.
1
K = κ1κ 2 = 7. There are two independent radius of curvature
R1 R2 and their directions are normal to each other.
Young-Laplace equation:simplified
derivation Butt et al
derivation. al. pp10
pp10. 2003
F = er Fn + et Ft

df n = 2σ dl sin α + 2σ dl sin β

sin α ≈ d / R1 ; sin β ≈ d / R2
⎛1 1 ⎞
dff n 2 d σ dl ⎜ + ⎟
⎝ R1 R2 ⎠
d π /2
⎛1 1 ⎞ 2 ⎛ 1 1 ⎞
Fn ∫0 ∫0 2 d σ ⎜⎝ R1 + R2 ⎟⎠ dθ dl = π d σ ⎜⎝ R1 + R2 ⎟⎠

Fn ⎛ 1 1 ⎞
ΔP = =σ ⎜ + ⎟ = ( 2H )σ
πd 2
⎝ R1 R2 ⎠
 Minimal surfaces (soap films):
Lagrange Nitsche
Lagrange, Nitsche, others
Lagrange: Lectures on a novel method for the
g formulae,, 1762
determination of maxima of integral
2 2
⎛ ∂z ⎞ ⎛ ∂z ⎞
z = z ( x, y ) ⇒ I ( ε ) = ∫∫ 1 + ⎜ ⎟ + ⎜ ⎟ dxdy
S ⎝ ∂x ⎠ ⎝ ∂y ⎠
Definition: A minimal surface is a surface whose mean curvature is zero
at every point of the surface.
Theorem: If there is a portion of a surface of minimum area among
all portions of surfaces bounded by the same closed curve, then the
surface is a minimal surface.
Minimal surfaces are sometimes defined as surfaces with the
property that any portion of them bounded by a closed curve has
the minimum area.
z xx 2 z x z y z xy z yy
2H = − +
2 1/ 2 3/ 2 2 1/ 2
⎡1 + ( z ) + ( z ) ⎤
2 ⎡1 + ( z ) + ( z ) ⎤
2 2
⎡1 + ( z ) + ( z ) ⎤
2
⎢⎣ x y ⎥⎦ ⎢⎣ x y ⎥⎦ ⎢⎣ x y ⎥⎦
 Static Contact Angles
Young’ss relationship (1805):
Young

“We
We may therefore inquire into the conditions of
σ SV − σ SL = σ VL cos θ o equilibrium of the three forces acting on the angular
particles, one on the direction of the surface of the
fluid only, a second in that of the common surface
off th
the solid
lid and
d fl
fluid,
id andd th
the third
thi d in
i that
th t off the
th
exposed surface of the solid. Now supposing the
angle of the fluid to be obtuse, the whole superficial
cohesion of the fluid being g represented
p byy the
radius, the part of which acts in the direction of the
surface of the solid will be proportional to the
cosine of the inclination; and its force added to the
force of the solid
solid, will be equal to the force of the
common surface of the solid and fluid, or to the
difference of their forces; consequently, the cosine
An Essay on the
added to twice the force of the fluid; will be equal
Cohesion of Fluids
to ....
Phil. Trans. Roy. Soc.
v. 95, 65-87
Interfaces are not 2D surfaces!
Interfaces are:
1.Diffuse (3D)
2.Dynamic
3 Asymmetric
3.Asymmetric
Macroscopic definition of contact angles

σ SV − σ SL = σ LV cos θ

•Young (1805) derived relation as

a balance of forces.

θs • Equation can be derived using

macroscopic arguments.
•Specific interfacial free energies
are macroscopic/thermodynamic
parameters.
• Contact angles are macroscopic
parameters and thermodynamic
functions.
 Surface forces of the second kind:
Derjaguin et al.
al Surface Forces,
Forces (1987) Plenum

Derjaguin and
Obuchov (1936)
At the contact line
line, there is an
interaction of molecular force
fields due to the presence of a
thi d phase.
third h
Forces of the second kind are the same
forces determining surface tension:
(1) Dipole-dipole, nonpolar or charge-
dipole interactions.(van der Waals)
((2)) Electrical double layers
y
(3) Structural forces induced by
molecular order.
 Augmented and Fully-augmented Young-
Laplace equation:
Static Jump-Momentum balance: Derjaguin
j g et al. Surface
Forces (1987)
Normal component: Teletzke, Davis and Scriven
(1988)
2 H gVL ( r , θ ) + ( p B − p A + Π ( r , θ ) ) = 0

Tangential component:
gVL ( r ,θ ) =
θ +δ L
= σ VL + ∫ ( Π ( r ,θ ) ) r dθ
θ δ
− L

Miller and The Young-Laplace

g p equation
q is valid awayy
Ruckenstein (1974)
from the solid surface where disjoining
Jameson and del pressure is negligible and surface tension is
Cerro (1976).
constant!
 MOTIVATION: molecular interactions
Derjaguin and Obuchov (1936)
• disjoining pressure
pressure, Π
[ ]
6 [ ]
6
ASL − ALL
Π=
6 π h3
• variable surface tension, gVL
d gVL
= −Π
Questions! dh
• Is Young's
Young s equation really valid?
• What is the proper definition for θ o ?
• How is θ o to be measured?
• Where is θ o located on the vapor/liquid interface?
Contact Angles (Merchant and Keller, 1992)

Used the method of matched asymptotic

expansions
i to
t validate
lid t Young’s
Y ’ equation!
ti !
™ Leading term in the outer expansion for the interface
shape satisfies the Young-Laplace equation.
™ Leading term in the inner expansion satisfies an
integral equation.
equation

™ Matched the two solutions and confirmed that

the slope angle – of the leading term in the
outer expansion is θo
-as given
i by
b Young’s
Y ’ equation.
i
 Interesting relationships for 2D systems:
L E.
L. E Scriven,
Scriven class notes UofM
UofM, circa 1980

dy
h = y ( x), tan θ =
dx
dy
sin θ = d
dx
2 1/2
2
2
d 2 y ⎛ dy ⎞ ⎡ ⎛ dy ⎞ ⎤
⎢1 + ⎜ ⎟ ⎥
d y
i θ ⎜ ⎟
d sin dx 2 ⎝ dx ⎠
= dx 2 −
1/2 2 3/2
= ⎢⎣ ⎝ dx ⎠ ⎥⎦
dx ⎡ ⎛ dy ⎞2 ⎤ ⎡ ⎛ dy ⎞ ⎤
⎢1 + ⎜ ⎟ ⎥ ⎢1 + ⎜ ⎟ ⎥ 1
⎢⎣ ⎝ dx ⎠ ⎥⎦ ⎢⎣ ⎝ dx ⎠ ⎥⎦ cos θ =
2 1/2
d2y ⎡ ⎛ dy ⎞ ⎤
= dx 2
= 2H
⎢1 + ⎜ ⎟ ⎥
⎡ ⎛ dy ⎞ ⎤ 2 3/2 ⎢⎣ ⎝ dx ⎠ ⎥⎦
⎢1 + ⎜ ⎟ ⎥
⎢⎣ ⎝ dx ⎠ ⎥⎦
 Macroscopic approach: ⎧de Gennes, Brochard,
⎪
⎨ Quere (2004) the
Two-dimensional
Two dimensional fluid wedge. ⎪ housewife
⎩ h if problem.
bl

Young-Laplace Equation: σ 2 H = − ( p L − pV ) , p L − pV = ρ g ( hC − h )
2 3/2
∂ h ⎡ ⎛ ∂h ⎞
2 ⎤
2 H = 2 / ⎢1 + ⎜ ⎟ ⎥
∂z ⎢⎣ ⎝ ∂z ⎠ ⎥⎦
Scriven, ChEn 8104 class notes (1982)
d cos θ dh
2H = − ; = tan θ
dh dz

d cos θ hC − h σ
= L =
2

dh L2C
C
ρg

hC h h2
cos θ = 2 − 2 + C {B.C. cos θ = 1 at h = hC
LC 2 LC
 Integrate and introduce one
boundary condition at a time:

hC h h2
cos θ = 2 − 2 + C {B.C. cos θ = 1 at h = hC
LC 2 LC
hC2
C =1 − 2
2 LC
hC2 hC h h2 hC2
cos θ = 1 − 2 + 2 − 2 ⇒ h = 0 ⇒ cos θ o =1 − 2
2 LC LC 2 LC 2 LC

Defines contact angle as the

Solution to Young –Laplace equation angle of intersection between
describes the gas-liquid interface of solution of YL equation and
a liquid puddle resting on a smooth, the solid surface
surface.
horizontal surface.
 Second method:

hC h h2
cos θ = 2 − 2 + C {B.C. cos θ = cos θ o at h → 0
LC 2 LC
C = cos θ o
hC h h2
cos θ o = cos θ − 2 + 2 ⇒ h = hC ⇒ cos θ =1
LC 2 LC

Defines
D fi contact anglel as the
h
Solution to Young –Laplace equation
angle of intersection
describes the gas-liquid interface of
between gas-liquid interface
a liquid puddle resting on a smooth,
and the solid surface.
h i
horizontal
t l surface.
f
 Consequences:
[1] Mathematical θ o is the B.C. at the solid
surface for solutions of the
definition of θ o
Young-Laplace equation
θ = θ o when
h h = 0

hC2
Fluid wedge: cos θ o =1 −
2 L2C

∗ match data points to a solution of the

Young-Laplace equation.
[ 2] Measurement of θo ∗ extend
t d the
th solution
l ti tot h=0
∗ measure the angle.
 MOTIVATION: Questions

Questions!
√ • Young's relation is macroscopically valid.
√ • θ o defined as B.C.
B C for YL equation.
equation
√ • θ o is measured intersecting YL with solid.

• Where is θ o located on the vapor/liquid interface?

Fluid Wedge: 3-region model
3-Region Model: Characteristic
Film Thicknesses

−3
hC ∼ 10 m
ht ∼ 3. 10−8 m
hm ∼ 10−10 m

hm
ε=
ht
ε ∼ 10−3 − 10−2
 Molecular region: Derjaguin
j g
gVL = specific interfacial free energy
[ 6] [ 6]
dgVL ALL − ASL
= −Π ( h ) =
dh 6π h3
[ ]
6 [ ]
6
A − A d gVL hm2
hm2 = LL SL
=σ 3
6π σ dh h
B.C. gVL → σ as h → ∞

⎡ 1 ⎛ hm ⎞2 ⎤
gVL ( h ) = σ ⎢1 − ⎜ ⎟ ⎥
⎢⎣ 2 ⎝ h ⎠ ⎥⎦

Note: gVL ≈ 0.995 σ when h = 10−9 m

 Transition Region: Null Curvature Point

2 H σ = − Π − ρ g ( hC − h )

⎧ Augmented
d cosθ h hC − h ⎪
2
− = − 2 ⎨Young-Laplace
m
3
dh h LC ⎪
⎩ equation

h2
hC ⎛ ht ⎞
m
= 2 ⎜1 − ⎟
3
At the null curvature point; h = ht , 2H = 0 ht LC ⎝ hC ⎠
2 2
ht / hC 1 h L
Since ht3 = m C
hC
 Transition region: Location of θο
d cos θ hm2 hC − h hC2
− = 3− 2 cos θ o =1 − 2
2 LC
dh h LC
BC h = hC ⇒ θ = 0

hm2 hm2 ⎛ h h2 ⎞
cos θ − cos θ o = 2
− 2 +⎜ − 2 ⎟ 2 (1 − cos θ o )
2 h 2 hC ⎝ hC 2 hC ⎠

At h = ht and θ = θt

hm2 ⎛ ht ⎞ ⎛ smaller ⎞
cos θt − cos θ o = 2
+ ⎜ ⎟ 2 (1 − cos θ o ) + ⎜ ⎟
2 ht ⎝ hC ⎠ ⎝ terms ⎠
2
3 ⎛ hm ⎞ 3
≅ ⎜ ⎟ = ε2
2 ⎝ ht ⎠ 2
 Transition region: Location of θ0
Where, on the vapor/liquid interface, is θo to be found?
3 2
cos θt − cos θ o ≅ ε
2

3
θ o ≅ θt + ε2
2sin θ o

⎧ since θ o > θt > θ

Nowhere! ⎨
⎩for all θ on interface

But: θ o ≅ θt to O ( ε 2 )
 Numerical Integration of FAYL equation
HEPTANE ON PTFE

*Continuous line: YL solution; Dotted line: FAYL solution

 CAPILLARY RISE: MACROSC0PIC APPROACH

2H σ = ρ g y
McNutt and Andes, J. of Chemical
Physics (1969)
Legendre transformation

d sin θ y⎫
2H = − = 2⎪ y2 Y 2 y
dy LC ⎬ 1 − sin θ = 2 = ⇐ Y=
⎪ 2 LC 2 LC
y → 0 ; sin θ = 1 ⎭
ρ g yo2 Yo2
cos θo = Y − (Y / 2 )
2
sin θ0 = 1 − = 1− ⇒ 2 2

2σ
o o
2
Capillary Rise: Molecular Approach

d cos θ ρ g hm2
− = y+ 3 {θ = θo at h = hS
dh σ h
2 hS
h y
cos θ o = 2
− ∫ 2 dh
m

2 hs ∞ LC

dh = ( dh / dy ) dy = − cot (π / 2 − θ ) dy = − tan θ dy

y tan θ dy Y −Y3 / 2
( )
y y
2 1/2
∫ =∫ dY = Y − (Y / 2 )
2 2

(Y )
2 1/2
2
− (Y / 2 )
0
LC 0 2 2

hm2
cos θ o ≅ YS2 − (YS2 / 2 ) + 2 = Yo − (Yo / 2 )
2 2 2 2

2 hs
 Molecular region: Further Analysis
d cos θ
gVL = −Π ( h )
dh
dgVL
= − Π ( h, θ )
dh
d gVL d cos θ
= − gVL ⇒ ln gVL = − cos θ + C
d h d h

⎡ 1 ⎛ hm ⎞ 2 ⎤ ⎧⎪ ⎡ 1 ⎛ hm ⎞2 ⎤ ⎫⎪
∗ But: gVL ( h ) = σ ⎢1 − ⎜ ⎟ ⎥ cos θ = − ln
l ⎨σ ⎢1 − ⎜ ⎟ ⎥ ⎬ + C
⎢⎣ 2 ⎝ h ⎠ ⎥⎦ ⎢⎣ 2 ⎝ h ⎠ ⎥⎦ ⎪⎭
⎪⎩
⎧ h = hL
∗ Determine C: ⎨ 4
⎩θ = θ L ⎛h ⎞
C = cos θ o + ln σ + O ⎜ m ⎟
⎝ hL ⎠
 −9
Molecular region: h < 10 m

4
⎡ 1 ⎛ hm ⎞ 2 ⎤ ⎛ hm ⎞
A[ ]
6
− A[ ]
6 cos θ = cos θ 0 − ln ⎢1 − ⎜ ⎟ ⎥ + O ⎜ ⎟
hm2 = LL ⎣⎢ 2 ⎝ h ⎠ ⎦⎥ ⎝ hL ⎠
SL

6π σ

∗ Gives θ = θ ( h, hm , θ o ) in molecular region.

∗ Proceed down to θ = 0!
h = hD ; θ = 0

⎡ 1 ⎛ h ⎞2 ⎤
cos θ o = 1 + ln ⎢1 − ⎜ m ⎟ ⎥
⎢⎣ 2 ⎝ hD ⎠ ⎥⎦
 Comparison with experiments:
Alkanes σ ASL ALL D θ exper. θ comp.
10-3 N/m 10-20 J 10-20 J 10-10 m (deg) (deg)
Heptane 20.3 4.03 4.31 2.979 21 20.8

Octane 21.8 4.11 4.49 2.811 26 25.8

Nonane 22.9 4.18 4.66 2.656 32 31.7

Decane 23.9 4.25 4.81 2.617 35 34.5

Undecane 24.7 4.28 4.87 2.501 39 38.7

Dodecane 25.4 4.35 5.03 2.489 42 41.8

Tetradec. 26.7 4.38 5.09 2.421 44 43.7

Hexadec. 27.6 4.43 5.22 2.402 46 46.2

 Conclusions:
Molecular Interactions ( close to the contact line )
⎧ gVL − surface
f tension
t i
give rise to variations in ⎨
⎩θ - slope of interface
s.tt θ → θo ⎫
⎬ as h → hL
gVL → σ ⎭

Macroscopic contact angle, θ o , is

• the B.C. for solutions of YL equation at surface h = 0
• obtained by matching data points to solutions
of the YL equation, extending the solution to h = 0
and measuring the angle.
• may or may not be found anywhere in the interface.